Monoazo acid dyestuffs



Patented Sept. 11, 1945 UNITED STATES PATENT OFFICE MONOAZO ACID DYESTUFFS Arthur Howard Knight and William Elliot Stephen, Blackley, England, assignors to 1mperial Chemical Industries "Limited, 'a corporation of Great Britain No Drawing. Application September :17; .1942 Serial No. 458,733. In Great Britain-Ontober 8,

1 Claim.

This invention relates to the manufacture of new mcnoazo acid dyestuffs and to their application to the colouring of animal fibres.

According to the invention We make the dyestuffs by diazotising an amine of the general formula in which R. stands for a benzene nucleus which may be further substituted with simple azo dyenstufi ,substituents, for example methyl, methoxy, or sulphon-ic acid groups, X stands for a monochloroor monobromo-alkyl radical with not more than three carbon atoms, Y stands for hydrogen, alkyl (C1 to C6), aralkyl, cycloalkyl, alkoxyalkyl or ary-l, and the primary amino group is in the meta or para position to the group, and coupling the diazo compound soobtained with a derivative of 2-amino-5-naphthol-l-s-ulphonicacid (J-acid) in whichone Hin the NHz group is replaced by a formyl, alkoxyformyl, succinyl, benzoyl .01 substituted benzoyl, iarylsulphonyl, hydroaromatic sulphony-lbr-hydroaromatic carboxyl group or an acyl group of general formula ---CO-( C11,H2n)O-B, wherein n stands ,for -1, 2 or 3 and R for alkyl (C1 to C4) ,ar-yl, cycloal-kyl or aralkyl, which aryl, cycloal-kyl and aralkyl groups may contain nuclear substituents', for example, methyl or halogen, and the other H in the NH? group may be replaced by an alkyl or aryl group.

Also according to the invention we use the dyestuffs in colouring animal fibres, e. g., wool and silk.

The dyestuffs dye woolfrom an acid bath, various shades of orange being obtainable; the dyeings are characterised by very good fastness to severe washing and milling and good fastn ess to light.

The following are examples of diazo components which may be employed in accordance with the present invention:

4-amino-1-N-ethyl-omega-chloroacetanilide, i-amino-1-N-isopropyl-omega-chloroacetanilidle, 4-amino-1-N-n-buty1-omega-chloroacetanilide, 4-am-ino-2-N-.ethyl-omegaechloroacet-toluidide, 4-.amino-2-N-ethyl-omega-bromopropion toluidide, 4-.amino-2-N-ethy-1-u-bromobutyryl-toluidine, B-aminoomega chloroacetanilide -4- sulphonic acid, 2 -.amino- 4-N-ethyl-omega chloroacet -t.o1uidide, -amino -.2 -N- ethy1- a-bromopropiontoluidi de,

4-amino-2-N-ethylomega chloropropiontolui- .dide, a 4-amino-1-N-ethyl-omega-chloropropionanilide', tampon-N-ethyl-omega-bromopropionanilide,

4-amino-1-N-sec-butyl-omega-chloroacetanilid'e,

4- amino. omega ehloroacetanilide-3-su1phonic acid, 4 amin0=2-N-ethylaomega-chloroacetanisidide, 4-amino-1-N-n-butyl-omega chloroacetanilide- ,2-sulphonic, acid, 4amino-1-N-ethyl-omega-bromoacetanilide, I 4-.amino-l -N-benz$1- megawhloroacetanilide,

4-amino-1-N-eyclohexyl omega chloroacetanilide, a t l 5-amino-2-N-cyclohexyl-omegarchloroacet-toluidide, e. 3-amino-1-N-benzy1-omega-chloroacetanilide, 4-amino-2-N- benz y1;omega:chloruacet-toluidide, 4-amino-1-N-phenylomega-chloroacetanilide,

eamino-lwNrcyclohexyl omega-ch-lbropropionanilide. p v 4-amino-l-N .c clohexyl-omega b romopropionanilide,

7 be employed according'to the invention, we mention:

2methoxyacetylamino-5 naphthol -'7- sulphonic iacid, l .zi-ethoxyaeetyiamino -5-naphthol '7- sulphonic acid 2-n-hutoxyacetylamino '-5 -'naphtholflesulphonic acid 2-;N ethyhN- nethoxyacetylamino-5=naphthol- '7-suiphonic acid e .2-Naphenyl N-methoxyacetylami'no-5-naphthol- H 'sul'prhonic :acid 2 stphenoxyacetyl') lamino-5-naphthol- 7-sulphonicaoid t Y a q; p 2; (a echlorophenpxyacetyl-l amino-S-naphtholil-sulphonicacid .r V t 2-(cyclohexyloxyacetyl). amino-5 naphthole7 sulphonic acid? 2-(p-phenoxypropionyl)-amino -5- naphthol -7- sulphonic acid 2-N ethyl-N-phenoxyacetyl-amino-5-naphthol 7-sulphonic acid 2-N- (2'-chlorophenoxyacetyl) N ethyl-amino- 5-naphthol-7-sulphonic 'acid phonic acid Z-formylamino-5-naphthol-7-sulphonic acid 2-succinylamino5-naphtho1 7- sulphonic acid 2-N-ethyl N succinylamino-5-naphthol-7-sulphonic acid 2-(2'-chlorobenzoyl)amino -5- naphthol 7- sulphonic acid 2-benzoylamino-5-naphthol-7-sulphonic acid 2-N-benzoyl N ethylamino-5-naphthole7-su1- phonic acid p 2- (benzene sulphonyl) amino-5-naphthol-7-sulphonic acid 2- (p-tolu'ene sulphonyl) amino-5-naphtho1-7-sulphonic acid 2 (tetrahydronaphthalene-2'-sulphonyl) amino- 5-naphthol-7-sulphonicacid 2-hexahydrobenzoylamino 5' haphthol-T-sulphonic, acid 2-isopropyloxyacetylamino -5- naphthol '7- sulphonic'acid agent, succinic anhydride, benzoyl chloride, benzene sulphonyl chloride, p-toluene sulphonyl chloride, tetrahydronaphthalene-2-su1phonyl chloride or hexahydrobenzoyl chloride respectively.

The invention is illustrated, butnotlimited, by the following examples in whichthe parts are -parts'of water and parts of 36% hydrochloric 2-N- (phenoxyacetyl) -N-ethylamino-5-naphthol- 2-N formyl- N-phenylamino 5-naphthol'-7- sulphonic acid 2 .(3-bromobenzoy1)amino-5-naphthol-7-sulphonic acid.

' N-alkoxyacyl, N- alkoxyacyl-N- alkyl and N-alkoxyacyl-N-aryl derivatives ,of 2-amino-5-naphthol-7-sulphonic acid are obtainable by interaction between the latter or the appropriate N- alkyl or N aryl derivative thereof, e. g., 2-N- ethylamino-5-naphthol-7-sulphonic acid or 2-N- Iphenylamino-5-naphthol- 7-sulphonic acid, and the chloride or anhydride of the required alkoxyfatty acid, e. g, methoxyacetyl chloride or methoXy-acetic anhydride,

N-aryloxy-,' -cycloalkoxyand -aralkoxy-acyl derivatives of 2-amino-5-naphthol-7-sulphonic acid (or a 2-N-alkylamino-5-naphthol-7-sulphonic acid) are obtainable by interaction between the latter and the required aryloxy cycloalkoxyor' aralkoxy-acyl chloride, e. g., phenoxyacetyl chloride, o-chlorophenoxy-acetyl chloride, cyclohexyloxyacetyl chloride and benzoyloxyacetyl chloride.

N-formyl, -succinyl, -benzoyl, -(benzene sulphonyl) (p-toluene sulphpnyl) (tetrahydro-- -naphthalene-2"-sulphonyl) and -h'exahydrobenzoyl derivatives of 2-amino-5-naphthol-'7-sul- -phonic acid (or a 2-N-aryl or -alkylamino-5- naphthol-7-sulphonic acid) are obtainable by interaction between the latter and formic acid in excess, or, in the presence of anaci d-binding "oii and dried.

acid and then a Solution of 6.9 parts of sodium 2'(benZy1XyacetyD ammolfina'phthpl S111" I nitrite in 50 parts of Water is added. The solution of'the dia'zo compoundso-obtained, after cooling to 5-10." C. is added to a stirred and cooled mixture of 33.3 parts 'of the sodium salt of 2- methoxyacetylamino -5- naphthol p-1- sulphonic acid, parts of sodium chloride, 350 parts of Water and 21 parts of anhydrous sodium carbonate. When coupling is complete, further sodium chloride is added to precipitate the dyestuif if necessarmand the latter is filtered of! and dried.

The new. dyestufi dyes wool from a dyebath containing sulphuric acid and Glaubers salt in reddish-orange shades, the dyeings having very good fastness to severe washing, milling and light. 7

' The coupling can also be carried out in the presence of other mild neutralising agents such as sodium bicarbonate or sodium acetate instead of sodium carbonate.

Example 2 22.6 parts of 4-amino-2-N-ethyl-omega-chloro acet-toluidide are dissolved in a mixture of 400 parts of water and 25 parts of 36% hydrochloric acid and to the solution at 5- l0 C. there is added a solution of 6.9 parts of sodium nitrite in 50 parts of water. The solution of the diazo compound so-obtained is added with stirring to a cooled mixture of 33.3 parts of the sodium salt of 2-methOxyacetylamino-5-naphthol-7-sulphon- 'ic acid, 80 parts of sodium chloride, 350 parts of water and 21 parts of anhydrous sodium carbonate. The new dyestuif so-obtai ned isisolated and dried.' It dyes wool in bright reddish-orange shades when applied from a'dyebath containing sulphuric acid and Glaubers salt, the dyeings having very good fastness to severe Washing, milling and light.

Example 3' 26.65 parts of 4-amino-l-N-cyclohexyl-omegachloroacetanilide are dissolved in a mixture of 350 parts of water and 25 parts of 36% hydrochloric acid. The solution is cooled to 1530 C. and 6.9 parts of sodium nitrite are added. The

solution of thediazo compoundis filtered, if necessary, and after cooling to 5-l0? C. is added with stirring to a cooled solution of 33.3 parts of the-sodium salt of 2-methoXyacetylamino-5- naphthol-l-sulphonic acid in 400 parts of water, to which sufficient sodium carbonate or sodium bicarbonate has been added to keep the coupling medium alkaline.

The new dyestufi, after precipitation by addition of sodium chloride if necessary, is filtered It dyes 'wool in dull reddishorange shades when applied from a dyebath containing sulphuric acid and Glauber salt, the dyeings having very good fastness to severe washing, .milling and light.

Dyestuffs having very similar properties are obtained if the z methoxyace'tylamino-5-naphthol-7-sulphonic acid is replaced by the equivalent weight of 2-ethoxyacetylamino-5-naphtholl-sulpho-nic acid or 2 butoxyacetylamino--naphthol-7-sulpho-nic acid.

Example 4 omegawhloroacet-toluidide there is employed the 5 same weight of 4"amino-lN-isopropyl omegachloroacetanilide'a dyestuff is obtained which yields on wool redder shades of orange, the dyeings having similar fastnes's properties.

Example 5 To an aqueous solution containing 'i23lfi-5-pants of sodium '4-amino-omegachloroacetanili'de-3- sulphonate are added 35 parts of 36% hydrochl'oric acid' followed by 6.9 parts of sodium nitrite. The solution of the diazo com-pound soobtained is added to a stirred mixture of 33.3 parts of sodium '2-methoxyacetylamino 5 naphthOl 'Z-sulphonate, 40 parts of crystallised sod-i um acetate and'450 parts of water at -1 5 C.

Stirring is continued until coupling is complete (about 1 hour) when the ne'w'deystufi isfiltered off, Washed with 10% aqueous sodium chloride and dried.

The new dyestuff dyes wool from an acid bath 'inscarlet shades, the dyeings having'very ood fastness to severe washing. milling, and light.

Example 6 28.5 parts of 4 amino Z-N ethy1 omega bromopropion-toluidide are dissolved in "Q06 parts of water and parts of 36% hydrochloric acid. Then 6.9 parts of sodium nitrite are added. The solution of the diazo compound so-obtained is added to a stirred solution at '10' l5 C. of parts of sodium 2 phenoxyacetylamino-5-haphth0l-7-su'1phonate in 600 parts'of water to which '28 parts of sodium acetate crystals have been added. VV'hen coupling is complete the new dyestuff is filtered off and'd'ried. a

The new dyestufij dyes wool from -a dyebath containing sulphuric acid and Glaubers salt in reddish orange shades of good fastness to severe washing, milling and light.

Dyestuffs having similar properties are obtained if the 28.5 parts of 4-amino-2-N-ethylomega-bromopropion-toluidide employed above are replaced by the same weight of 4-amino-2- Nethyl-a=bromopropion-toluiclide or by'24 parts of 4-amino-2*N-ethyl-omegaechloropropion toluidide.

Example 7 To a solution of 25.65 parts of 4-aminO-l-N- I [3-ethoxyethyl-omegacli1oroacetanilide in 300 parts of water and 25 parts of 36% hydrochloric acid are added 6.9 parts of sodium nitrite. The

solution of the diazo compound so-obtained is added gradually to a stirred solution at 10-l5 C. of 33.3 parts of sodium 2-methoxy-acetylamino- 5-naphth0l-7-sulphonate in 500 parts of Water to which have been added :28 parts of sodium .ace-

22.65 parts of 4-.amino-l-N-isopropyl omegachloro-aceta-nilide are dissolved in-EGO parts of water and 25 parts of 36% hydrochloric acid and 6.9 parts of sodium nitrite are then added. The solution of the di-azo compound so obtained is gradually added to .a stirred solution of 40.9 parts of sodium '2-benzyloxyacetylamino-5-naphthol-7- sulphonate and 28 parts of crystallised sodium acetate in 650 parts of water. When coupling is complete the. new dyestufl is filtered off, washed with 5% aqueous sodium chloride and dried.

.It dyes Wool from an acid bath in orange shades, the .dyeings having very good fastness'to severe washing and milling and good fastness to light.

Eciample 9 21.25 parts of 4-amino-LN-ethyl-Omega-chloroacetariilide are dissolved in a mixture of 300 parts of water and 25 parts of 36% hydrochloric acid'and to the resulting solution there is added a solution of 6.9 parts of sodium nitrite in 50 parts of water.

The solution of the diazo compound soobtained is cooled to 5-10 C. and added to a cooled and stirred mixture of 36.5 parts of the sodium salt of 2-benZoyl-amino-5-naphthol '7-sulphonic acid 5'00 parts of water and 21 parts of anhydrous sodium carbonate. Coupling is completed very quickly. The dyestufi is salted out with sodium chloride if necessary, filtered oil and dried.

The new dyestuif forms areddish orange 'powder. soluble in water, anddyes wool from an acid bath in reddish-orange shades, the'dyeingshaving' very good "fastness to severe washing and milling.

The coupling can also be carried out: in the presence of other mild acid-binding agents such as sodium acetate or sodium bicarbonate instead of sodium carbonate. p

. Example 10 v 22.6 parts of 4-a-mino' Z-N-ethyl-0mega-chloroacet-toluidide are""dissolved in a mixture of 400'parts of water and 5 parts"of"36%' hydrochloric acid and diazotised at 540? 'Cmby the addition of a solution of 6.9 parts of sodium nitrite'in' '50 parts of water. The solution of the diazo compound so obtained is added gradually to a cooled and stirred solution of 39.3 parts of the sodium salt of 2-N-benzoyl-N-ethyl-amino- 5-naphthol-7-sulphonic acid in 600 parts of water to which have been added 21 parts of anhydrous sodium carbonate.

The new dye-stuff is isolated and dried. It

dyes wool from an acid bath in, reddish-orange shades, the dyeings having very good fastness to severe washing, and milling, and good fastness to light.

Example 11 22.65 parts of 4-amino-1eN-ethyl-omega-chlm ropropionanilide are dissolved in 350 parts of waof 41.5 parts of the sodium salt of 2-(p-toluene sulphonyl)-amino--naphthol-7-sulphonic acid, 600 parts of water and 28 parts .of crystallised sodium acetate. When coupling is complete the new dyestuff is isolated and dried.

The new dyestuff dyes wool from a dyebath containing sulphuric acid and Glaubers salt in reddish orange shades, the dyeings having good fastness to severe washing, milling and light.

A dyestuff having similar properties is obtained if 27.1 parts of 4-amino-l-N-ethyl-omeg'a-bromm propionanilide are used instead of the 22.65 parts of 4-amino-1-N-ethyl-omega-chloropropionanilide. 7 Example 12 26.65 parts of. 4-amino-1-N-cycloheXyl-omega chloroacetanilideare dissolved in a mixture of 350 parts of warm Water and 25 parts of 36% hydrochloric acid. The solution is cooled to -30 C. and 6.9 parts of sodium nitrite are added. The solution of the diazo compound is filtered, if necessary, and after cooling to .5-10 C. is added gradually to a stirred and similarly cooled solution of 33.3 parts of sodium Z-ethoXyformylamino-5-naphthol-7 sulphonate in 600 parts of water to which 28 parts of sodium acetate crystals have been added. Stirring is continued until coupling is complete. Thesuspension of the new dyestuff is'then rendered alkaline with sodium carbonate, the dyestuff filteredofi, washed with 5% aqueous sodium chloride and dried.

The new dyestufi forms a reddish orange powder, soluble in water, and dyes wool from a dyebath containing sulphuric acid and Glaubers salt in orange shades, the dyeings having very good fastness to severe washing and milling and good fastness to light.

If the equivalent weight of sodium 2-benzenesulphonylaminoor 2-(p-toluene sulphonyl)- amino-5-naphthol-7-sulphonate is used in place of the sodium 2-ethoxyformylamino-5-naphthol- 7-sulphonate, dyestuffs yielding somewhat redder shades of orange and having similar fastness properties are obtained. 4

I Example 1 3 salt of 2-succinylamino-5-naphthol-7-sulphonio acid containing excess of, sodium carbonate.- The dyestufi so obtained is precipitated by addition -of sodium-chloride, filtered off, washed with aqueous sodium chloride and dried.

The new dyestufi forms a dull scarlet powder, soluble in water, and dyes Wool from an acid bath in reddish orange shades, the dyeings having very good fastness to severe washing and good fastness to light.

A dyestuil yielding slightly redder shades and having very similar fastness properties is obtained if the disodium salt of 2-succinylamino-5- naphthol-7-sulphonic acid used above is replaced by 36.5 parts of the sodium salt of 2-benzoylamino-5-naphthol-7-sulphonic acid.

Example 14 27.45 parts of 3-amino-l-N-benzyl-omegachloroacetanilide are dissolved in 400 parts of water and 25 parts of 36% hydrochloric acid and 6.9 parts of sodium nitrite added. The solution of the diazo compound so-obtained, after filtration if necessary, is added to a stirred solution at 10-15 C. of 44.3 arts of the sodium salt of 2- N-(p-toluenesulphonyl) -N-ethyl-amino-5- naphthol-7-sulphonic acid in 400 parts of water to which 28 parts of sodium acetate crystals have been added. When coupling is complete (after about 4 hours) the precipitated dyestufi is filtered off, washed with 5% aqueous sodium chloride and dried.

The new dyestufi forms a reddish orange powder, soluble in water, and dyes wool from an acid bath in orange shades, the dyeings having very good fastness to severe washing, milling and light.

If the sodium salt of Z-N-(p-toluenesulphonyl) N-ethylamino-S-naphthol-'7-sulphonic acid is replaced by the corresponding weight of sodium 2- N (p toluenesulphonyl) N methyl-amino-5- naphthol-7-sulphonate, a dyestuff having similar properties is obtained.

Example 15 To a solution of 34.25 parts of the sodium salt of 4 amino-1-N-n-butyl-omega-chloroacetanilide-2-sulphonic acid in 200 parts of water are added 35 pants of 36 hydrochloric acid and then 6.9 parts of sodium nitrite. The solution of the diazo compound so-obtained is filtered if necessary and then added at 10-15 C. to a stirred solution of 28.9 parts of the sodium salt of 2-formylamino-5-naphthol-7-su1phonic acid in 500 parts of water to which 40 parts of sodium acetate crystals have been added. Coupling is rapid and, when complete, the dyestufi' is precipitated by addition of sodium chloride, filtered off and dried.

The new dyestuff dyes wool from a dyebath containing sulphuric acid and sodium sulphate in yellowish orange shades, the dyeings having good fastness to severe washing, milling and light.

The invention is further illustrated by the examples listed in the following table:

Example q N0. e i m comment fi d ifitipiifi 333353129302? 16 3-aminp-omega-chloroacetanilidc-4-sulphon- Z-methoxyacetylamino-5 naphthol-7-sul- Sodium acetate Orange 10 ac v phonic acid. l7. 4-ammo-l-N-ethyl-omega-chloroacctanilide 2-N-methoxyacetyl-N-ethylamino-5-naphdo Reddish-orango I thol-T-sulphonic acid. l8 4-a' mmo-l-N-ethyl-omega-chloropropionani- 2-methoxyacetyl-amino-S-naphth0l-7-sul- ..,do Do hd i phonic acid. n 19 do 2-pg o yaqg yli o- -napht ol-7-sul- Sodium carbonate. Do.

p onic aci 20 4-a1: m no-2-N-ethyl-omega-chlotoprop1on-t0l- 2-(2-chlorophenoxy o iyl)- mino-5-naphdo Do.

uidide. thol-7-sulphonic acid. n 21 dc 2-n hpxyao yl mino-5-11aphthol-7-sul- Sodium acetate. Bright reddish V p ouic ac] 22 4-a mmo-l-N-cyclohexyl-'on1ega-chloroacetan- 2-N- (phenoxyacetyl) -N -etl1ylamino-5- Sodium carbonate. R zi iffi-orange e. naphthol-7-sulphonic acid. 23 4-ammo-1-N phenyl-omega-chloroaoetamlide. 2-mlethoxyacgtylamino-5-naphtl1ol-7-sul- Sodium acetate D 11 ll 1' e d d i s hp 0111c aci 24 4mnmc-z-N-benzyl-omegarhloroacet-tolui-- do do Ogg g e e. "n 25 s-amino-l-N-benzyl-omega-chloroacetanilidc. do; do D Example Acid binding agent Shade given by the No Dlazo component Coupling component used in coupling dyestufi on wool 26 4-amino-1-N-isoptopyl-omega-chloroacetani- 2-N-methoxyzcety1-N ethylamino-5-naph- Sodium acetate Orange.

iide. tho1-7-sulphonic acid. 27 .do Z-N-methOXyacetYI-N-phenylamino- 5 Sodium carbonate. T) u 11 r e d dish naphthol-7-sulphon1c acid. orange. 28 4-amin -1-N- b tylg hl t 2-methoxya oety1amino-5-naphtho1-7 -su1- Sodium acetate... B right reddish ilide. phomc acid. orange. 29 ..do 2- (phenoxyacetyi) -am1no-5-naphtho1-7- ..do Orange.

sulphonic acid. 30 .d0 2-isopropyloxyacetylamino-5-naphthoi-7- do Bright reddish.

sulphonic acid. orange. 31 4-amino-l-N-ethyl-omega-chloroacetanilide. 2- c c1ny1am1no-5-naphth01-7-suiphonic do Orange.

aci 32 do 2-(2-ch10r obenz0y1)-amino-5-naphtho1-7- Sodium carbonate. Reddish orange.

suiphonlc acid. 33 4-amin0-l-N-ethyl-omega-chloroacetaniiide 2- -(2-0h1 r0 z0s 1)- -ethy1amin0-5- do Do.

naphtho1-7-suiphomc acid. 34 do 2-(p-toluene-sulphonyl)amino-duaphthoi- Sodium bicarb n- Do.

7-sulphomc acid. ate. 35 do 2-ethoxyformylamino-5-naphtho1- 7-sui- Sodium carbon t Orange.

phonic ac1d 7 3G 4-amino-1-N-isopropy1-omega-chloroacetan- 2- 11%=1ny1 m1 Dh -7- 1lph0nic -d0 D0.

1 e. aci 37 4-aminO-Z-N-ethyl-omega-chloroacet-toiuidide Sodium acetate. Bright orange. 38 do 2- (2-oh1orobenzoylam1no- 5-naphtho1-7- Sodium c b n D suiphonic acid. 39 4-al! 1 1iino-2-N -etl1yi-omega-ch1oropropionan- 1 Sodium acetate... Do.

1 1 e. 40 4-amin0-l-N-benzyl-omoga-chloroacetaniiide. z-eg xyf p yla p t ol-7-su1 .do Reddish orange.

p 01110 acl 41 4-5111in0-1-N-phenyl-omega-chloroacetani1ide 2- -bc oy}- -e y i o- -naphthol- .--.-do Dun scarlet. 7-sulphon1c acid. 42 d 2-N-formy1-N-pheny1-amino-5-naphtho1- ..do D

, 7-su1 phonic acid. 43 4-ainino-2-N-benzyl-omega-chloroace 2-su5g31nylamm0-5-naphtb017 -sulphonic Sodium carbonate. Scarlet.

i e am 44 4 amino 1 N sec butyl omega hl 2 :benaoylammo 5 -naphtho1- 7 -su1phon- Sodium acetate. Reddish orange.

acetaniiide. 1o acid. 45 4 amino 1 N n butyl omega chloro- Z- BX Y P Q Y 5 naphtholdo Orange.

acetanilide. 7-sulphon1o acid. 46 3 amino omega chloroacet anilide 4 2 N Y -N WW- o 5 ph- ...do Brownish orange,

sulphgnic id tho1-7- sulphon1c and. 47 3 -amino -omega-ch1oropropionanilide -4- 2 SHOQIDYXBJHIIIO 5 Haphflml 7 8111- do Yellowish orange.

sulphonic acid. phonlc acid. 48 4 amino 1 N oyclohexyl omega chloro- 2 formylamino 5 naphthol 7 sulphon- SOdIHm carbonate- Reddish orange.

acetanilide. 1c acid. 49 d 2 (2 chlorobenzoyl) ammo 5 naph- ..do D

' tho1-7-su1phomc acid 5o do 2 (3' bromobenzoyl) ammo 5 naph- Sodium acetate. D

tho1-7-sulphomc acid. 51 4 amino 1 N cyclohexyl omega chioro- 2- ahy ro ap -2 lp1}0ny1)- Sodium carbonate. Do.

ao tanilid amino-5-naphtho1-7-suiphomc acid 52 z-N-formyl-N-phenylammo-5-naphtho1-7- V e r y r e d d 1 s h suiphomp acid. orange. 53 do 2 -N-succmy1-I I-e hy1-ammo 5-naphdo thoi-muiphoniq acid. 54-... 4 amino 1 N -cyc1ohexy1-omega-ch1oro- 2-N -succ1ny1ammo 5 -naphtho1- 7 -su1- Sodium acetate- Reddish orange.

propionanilide.

phonic acid.

We claim: .The azo dye which in the form of its acid is represented. by the formula H033 I H H O N=N ARTHUR HOWARD WIGHT. WILLIAM ELLIOT STEPHEN. 

